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Functionalized Polyoxovanadates: Synthesis, Characterization and Properties
Title
Functionalized Polyoxovanadates: Synthesis, Characterization and Properties
Creator
Zheng, Yujuan
Date
2012-04-30, 2011-12
Description
The compound [NaVIV6O6{(OCH2CH2)2NCH2CH2OH}6]Cl.H20, designated C0 in this report, an Anderson type structure, contains a single nitrogen atom...
Show moreThe compound [NaVIV6O6{(OCH2CH2)2NCH2CH2OH}6]Cl.H20, designated C0 in this report, an Anderson type structure, contains a single nitrogen atom in place of a single oxygen atom in each of the six vanadium-oxygen octahedra. Attached to each nitrogen are two alkoxide arms (-O-C-C-) which terminate on separate oxygen atoms of the octahedra. A third ethoxy group (-CH2-CH2-OH) dangles freely from each nitrogen atom. The functionalized cationic core [NaVIV6O6{(OCH2CH2)2NCH2CH2OH}6]+ is generated in situ and is cationic with a charge of +1. Chloride is the counteranion. Each vanadium addenda atom is the +4 oxidation state, and the six unpaired electrons result in interesting magnetic properties. C0 is obtained by reaction of a vanadium oxide source triethanolamine. The purpose of the research described here was to adapt the synthetic protocol associated with triethanolamine to other similar ligands. Ligand choice was motivated by the broader goal of this research group to form (extended) hybrid electronic and magnetic materials by chemically bonding POM cores to chemically interesting ligands, such as dyes or other POM cores. In this regard, the original triethanolamine derivative has a number of shortcomings; chief among them is the inaccessibility of the alcoholic functional group chemistry---due to its low pH---that otherwise might have been used to form linkages through the dangling alkoxy arms. Additionally, linkages containing paraffinic carbon (-C-C-), which is not a good conduit of electronic interaction, are chemically undesirable where the synthetic goal is hybrid structures with interesting electronic and magnetic properties. The results associated with the three ligands, diethanolamine, N,N'-Bis(2-hydroxyethyl)ethylenediamine, and N,N-Bis(2-hydroxyethy) ethylenediamine, are described herein. Diethanolamine was chosen because---based on a structural comparison to triethanolamine---it was expected to produce a structure having a hydrogen atom in place of the dangling ethoxy arms, which was indeed the result. We considered this structure highly desirable becasue of the potential lability of the hydrogen atom (-N-H), which would allow us to functionalist the core directly. The resulting compounds are characterized by single-crystal X-ray diffraction, elemental analysis, mass spectroscopy, thermogravimetric analysis, FT-IR and UV-Vis spectroscopy, maganometric titration, temperature-dependent magnetic susceptibility measurements, and cyclic voltammetry. The results of the cyclicvoltammetric investigation are consistent with the labile hydrogen atom (-N-H).
M.S. in Chemistry, December 2011
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